Novel vinyloxyalkylamidonitriles, polymers thereof, and their production



u te s atem NOVEL VINYLOXYALKYLAIVIIDONITRILES, POLYMERS THEREOF, AND THEIR PRO- DUCTION Leo S. Luskin and Peter L. de' Benneville, "Philadelphia, Pa., assignors to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware Application November 29, 1955 Serial 'N0., 549,851

14 Claims. cl. 2 -855 N 0 Drawing.

where Z is an alkylene group having 2 to 6'carbon atoms, the oxygen and the-nitrogen being attached to different carbons thereof, A is selectedv from the group consisting of cyclohexylidene,

where R is an alkyl group having 1 to 8 carbon atoms, and

where R is selected from the group consisting of methyl and ethyl, and R is as just defined, and R is selected from the group consisting of H, alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to carbon atoms, including phenyl, naphthyl, alkylphenyl-in which the alkyl group has 1 to '4carbon atoms, halogenated phenyl and naphthyl groups, especially those containing chlorine or bromine, benzyloxy, and alkoxy and alkoxyalkyl groups of the formulas R 0- and R OR where R and R are selected from the group consisting of the same and different alkyl groups having 1 to 4 carbon atoms; with the proviso that when R is H, the two; carbon atoms in A and Z that are attached directly to'the N atom therebetween each carry two hydrogen atoms. I

The compounds of Formula I are obtained from aminonitriles of Formula II:

(II) CH CHOZNHACN where Z'and A are as defined above. These aminonitriles are obtained by reacting an aminoalkyl vinyl ether of Formula III:

(HI) CH CHOZNH with a member selected from the group consisting of alkylene cyanohydrins of the formula HOACN, including ketonecyanohydrins of the formula 2,833,751 Patented May 6, 1958 ice wherein R and R are as defined .hereinabove, and aldehyde cyanohydrins of the formula R being as defined above, also acryolnitrile, methacrylonitrile, and crotononitrile.

Examples of the vinyl esters of Formula III include:

Examples of cyanohydrins are those of formaldehyde, I

acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, caprylaldehyde, and pelargonaldehyde, acetone, ethyl methyl ketone, diethyl ketone,

methyl isopropyl ketone, ethyl n-propyl ketone, methyl"- butyl ketone, methylhexyl ketone, etc; 1, .v

The reaction between the cyanohydrin and the amine of Formula III may be carried out in the absence of a solvent, but is generally eflected in the presence of water. or in non-reactive solvents, such as benzene, toluene, xylene's, petroleum ether, ether, diisopropyl' ether, dibutyl ether, dioxane, ethanol, methanol, isopropanol, etc. The amine of Formula HI and the cyanohydrin are preferably employed in equimolar or substantially" ,equimolar amounts. Instead of introducing a preformed. cyanhydrin into the solution of the amine, the cyanohydrin maybe prepared in situ inthe reactionmedium. in the presence of the amine of Formula III by thea'ddi-fl tion of .equimolar amounts of hydrogen cyanide and, ether, and aldehyde or ketone, The cyano'hydringis produced rapidly and then reacts with the amine.- 'Thej reaction is effected at a temperature of 0 to 50 C; It; is exothermic in character and may take various periods oftime depending on the particular temperature and.v the particular reactants. Generally, f4 to 24 hours standing is adequate. Water is split out as a by-product are distillable and may be purified in this mannerf- Those obtained from ketone distillable. Y r I In the reaction of the amine of Formula III with an unsaturated nitrile, specifically acrylonitrile, methacrylonitrile, and crotononitrile, the reactants are-utilized in; equimolar or substantially equimolar amounts, although; an excess of either may be present, The use of solvents cyanohydrins are generally not for this reactionis optional. If desired, such solvents;

may be used as t-butanol, acetonitrile, nitromethane, and chlorinated solvents, such as chloroform; carbon tet-, rachloride, and ethylene dichloride. If desired, -,an ex; cess of the amine of Formula 1]] may-be used;.as"a ;sol-

vent. The reaction maybe eifected at a temperature,

' of cellulosic type, such as rayon andcotton. They may be used as components of shoe polish and of textile dressings and sizes. They are useful as intermediates for producing many other useful compounds of a wide variety. Thus, they may be reduced to produce amino groups in place of the nitrile groups. They react with alcohols to produce acetals and they are also reactive with dicyandiamides to produce' new acyl guanamines which are described and claimed in our copending application Serial No. 549,852, filed on even date herewith. The monomeric compounds are also adapted to be polymerized in bulk by means of boron fluoride ether-ate. They may be copolymerized with-other known polymerizable comonomers by bulk, solution, aqueous emulsion procedures or suspension procedures. For this'purposegfree radical catalysts of the azo type are useful including azodiisobutyronitrile, dimethyl azodiis'obutyrate and so on. They. may thus be copolymerized with other monoethylenically unsaturated compounds including'esters of acrylic acid, such as methyl acrylate, ethyl acrylate, butyl acrylate, 2- ethylhexyl acrylate, 3,5,5trirnethylhexylacrylate, dodecyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, phenoxyethyl acrylate, cyclohexylacrylate, benzyl acrylate, and the like, acrylamides, acrylonitrile, methacrylonitrile, esters of methacrylic-acid including methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, cetyl, ethoxyethyl, butoxylethyl, cyclohexyl, benzyl, anddimethylaminoethyl methacrylates, vinyl esters such as-vinyl acetate, ureidoethyl vinyl ether, styrene, and vinylpyridine.

The polymers, and-especially thet copolymers, are useful as components of adhesives, coatings, textile finishes and the like. 7

benzene (300 ml.) is added and. the water layer is sepa- Freshly distilled lactonitri1e"(213 grams, 3 moles) is added during a period of 30 minutes to fl-aminoethyl vinylether (261 grams, 3 moles) at room temperature. Stirring is continued for 5 hours. Benzene (400; ml.) is

added and the water layer is separated. Distillation of.

the benzene layer gives 366 grams -(an'87%,yield) of a-f [-N-B-vinyloxyethylamino] -propionitrile as a pale'yellow oil boiling in the range, 651 10 6 9 C./0.2 mm. Hg, 12 =1.45O3. Anal. Calculated: N, 20.0%. Found: N, 19.7%.

Example C alsobutyral-dehyde .cyanohydrin (99 grams, 1 mole) is added slowly to B-aminoethyl vinyl .ether -('87 grams, 1 mole) at ,25 9 to 30 C. After stirring for-5 hours, the water layer is removed-why the addition of 200 ml of henzene. The 'benzene is distilled to give 115.71 grains of a yellow residual oil. Further distillation gives 151 grams (a 93% yield) of wl N p-vinyloxyethylaminol -isovaleronitrile. as.a colorless oil boiling ,in vthe range 77 to 82 C."/ 0.6 mm. -Hg,- n =1-.4490L Calculated: N, 16.7%. Found: N,16.6%- V Freshly distilled acetone cyanohydrin ('85 grams, 1 mole) is added to p-aminoethyl vinyl ether (87 grams, 1 mole) in 10 minutes at 25 to 40 C. The mixture is cooled in an ice-bath as needed and stirred at 25 to 30 C. for 3 hours. Chloroform (150 ml.) is then added to separate. the water. Evaporation of the chloroform at reduced pressure leaves 144 grains of u-l-N-fi-v-inyloxyethylamino]-isobutyronitrile as a colorless oil,

Anal. Calculated: N, 18.2%. Found: N, 18.2%

Example E Cyclohexanone cyanohydrin (25 grams) is added to a solution of fi-aminoethyl vinyl ether (17.4 grams) in benzene (100 ml.) in 15 minutes at 20 to 32 C. The temperature is controlled by the rate of addition of the cyanohydrin and no external cooling is required. The mixture is stirred for two hours. The benzene layer is separated from the small water layer and evaporated under reduced pressure below C. to give 21.5 grams of 1-[,B-vinyloxyethylamino]cyclohexanenitrile as a yellow oil, n =l.4"/'77. Anal. Calculated: N, 14.4%. Found: N, 14.0%.

Example F (a) Acrylonitrile (106 grams, 2 moles) is added, with cooling, to aminoethyl vinyl ether (174 grams, 2 moles). After 6 hours, volatile material is evaporated with a water aspirator on the steam bath. The orange oily residueweighs 250 grams (an 89% yield), N 20.0% by analysis. e

Distillation gives 196 grams (a yield) of fl-N-flvinyloxyethylaminopropionitrile as a colorless product boiling in the range 79 to 81 C./0.4 mm. Hg and 46.5 grams orange residue. The colorless product had an N =1.4599 and an 'an'alysis of' 19.8%' N. Theory 20.0% N.

(b) By the procedure of part (a) substituting 2 moles of methacryloni-trile for acrylonitrile, a-methyl-p-(N- vinyloxyethylamino)-propionitrile is obtained in good the acrylonitrile with crotononitrile produces 'fi-(N-vinyl-t Example G Hydrogen cyanide (54 grams) is added to a solution in 650. cc. of 95% ethylalcohol of 186 grams of cyclo hexanone and 175 grams of: fl-aminoethyl vinyl ether. The mixture is maintained at room temperature and there 1 is isolated by the procedure described in Example E above, the product 1-(N-fi-vinyloxyethylamino)-1-cyclohexanenitrile.

, Example H To a solution othydrogen cyanide (81 grams, 3 moles) 1 and piperidine (5 ml.) in diethylether (200 ml.), isobutyraldehyde (144 grams, 2 moles) is added in 1 hour. The reaction flask is cooled with an ice-water bath to maintain the temperature below 25 C. The reaction is allowed to stand for 3' hours. Aminoethyl vinyl ether (174 grams, 2 moles) is then added in 2 hours at 25 to 30 C. The reaction mass is allowed to'stand overnight. Benzene is added to help the separation of water. The oil layer is distilled to give 258 grams (a 77% yield) of ot-[-N- 8-vinyloxyethylamino]eisovaleronitrile as a pale yellow oil boiling in the range to C./ 0.9 mm. Hg. Anal. Calculated: N, 16.7%. Found: N, 16.4%.

lExanipleJ v Acetyl chloride (39.3 grams, 0.5 mole) is added slowly I to a solution of a-N-fi-vinyloxyethylaminopropionitrile m-4am.

i 1 (70 grams, 0.5 mole) and't'riethylamine (50.4 grams, 0.5 mole) in benzene (150 m1.) at 15 to 25"- C. with cooling. Stirring is continued :overnight. Triethylami-ne hydrochloride is collected, washed with benzene and dried; it

Methyl forinate (120 grams, 2 moles) and N-B-vinyloxyethyl'aminoacetonitrile. *(120 grams, 1 mole) are heated together under gentle reflux at 40 C. for 8 hours. Evaporation of the excess ester under reduced pressure gives 150 grams (calc. 154 grams) of N-(B-vinyloxy ethyl)formamidoacetonitrile as a residual brown oil, N 18.0% and 18.2% found (calc. 18.2%).

Example 3 propionitrile weighs 183 "gram'sfa 97% yield). Distillation gives a 90% yield of the essentially pure product as a yellow oil, boiling. in h the range of 107 -to 112 C./0.2 mm. Hg.

Example 4 By the procedure of Example 1, 'acetyl chloiide is reacted. with l N B-Vinyloxyethylaminoacetoni(rile producing a 62% yield of N-fl-vinyloxyethylacetamidoacetonitril'e boiling in the range 113 to 125 C./0.25 mm. Hg, n ==1.4760, 16.4% N by analysis (16.7% N calci).

Example 5 l (a) By the process of Example 1, benzoyl chloride. (.05 mole) is reacted with a-.(N-p-vinyloxyethylamino) propionitrile (0.5 mole) producing a-(N-pwinyloxyethyl benzamido)prop'ionitrile having n =L5286 and a nitrogen analysis of 11.2% (11.5% .c'alc.) before distillation. (b) Part (a) is repeated replacing the nitrile reactant with a-(N-fl-vinyloxypropylamino)propionitrile producing the compound v(N-fi-vinyloxypropylbenzamido)propionitrile.

Example 6 By the process of Example 1, propionyl chloride (0.5 mole) is reacted with p-N-p-vinyloxyethylaminopropionitrile (0.5 mole) producing in 50% yield the product fl- N-fl-vinyloxyethylp ropionamido] propionitrile.

Example. 7

Example 6 is repeatedsubstituting 0.5 mole of benzoylchloride for the propionyl chloride, yielding p- [N-fl-vinyh oxyethylbenzamido]-propionitrile. Found 11.2% N (11.5% calm); p

1 Example 8 h (a) By the process of'Exainple 1, acetyl chloride "(0.5

mole) is reacted with 0.5 mole of a-[N-fl-vinyloxyethylamino]-isovaleronit rile of the formula producing U a 'l N-fi-vinyloxyethylacetamido -isovaleronitrile of the Formula IV:

oHi=ciiocH2cmN oH cN 1:0

(1v) Ha (b) The process of part (a) hereof is repeated, substituting for the nitrile (reactant in successive runs,

(1) The nitrile of part (b) (1) of Example A. (2) The nitrile-ofpart (b) (2) of Example A. (3) The nitrile of part (b) (3) of Example A.

Example 9 By the process of Example 2, 2 moles of methyl formate are reacted with 1 mole of 13- [N-fi-vinyloxyethylamino]- prop'ionit'iile, producing fl- [N-fl-vinyloxyethylformamidoZl propionitrile, having rif -1.4880 and analyzing 16.5% N (16.7% N can).

Example 10 Palmitoyl chloride "(69 grains, 0.25 mole) is added to a solution of; .p [N-fi-vinyloxyethylainino]-propionitrile (35fgi'ams,-'0.2 5 mole) in pyridine (65 ml.) in 1% hours at 27 to"42 C. "Cooling is used to keep the temperature below 42 C. An equal amount of pyridine then added to: facilitate stirring, which is continued .for 2% hours. The filtrate is dissolved in 250 ml. of benzene and washed five times with 100 ml. portionsof water. The benzene is distilled under reduced pressure to give 78.5 grams (86% "offafdark 'oil'which solidifies to a tan wax. Catalytic hydrog nation proves that the vinyl group is intact, for practically 1 mole of gas is absorb'ed. Anal. Calcu- 7 Example 11 By the procedure of Example 2, methyl methoxyacetate (2 males) is reacted with -1 mole of a- [N-p-vinyloxyethylaminoldsovalei onitrile producing a 93% yield of a compound of formula V:

HaO* CHs caponocnionm- H-ON =0 (V) HIOCHI Found 11.9% N; 11.7% (calm).

' Example 12 VI) (31H! (b) Part (4.) hereof is repeated, substituting for the nitrile reactant, ine'ach of several runs,

(1) The nitrile of part ('b) (1) of Example A.

(-2 )'T1ie nitrile of part '(b) (2) of Example A.

(3) The nit'file of part (b) (3) of Example A.

Example 13 7 By the procedure of Example 3, ethyl chloroforiirat'e (1 mole)"i's reacted with 1 mole of a-N-p-vinyloxyethylaminopropionitrile producing a compound having the Pyridine hydrochloride is removed by filtration.

9 Formula VII having n =1.4525 and 12.9% N (13.2% N calc.):

GHFCHOGHICH2N -OH(CHS)ON Example 14 (a) By the procedure of Example 3, ethyl chloroformate (1 mole) is reacted with 1 mole of a-[N-fl-vinyloxyethylaminol-isovaleronifi'ile producing a 97% yield of an oil boiling in the range 85 to 90 C./0.15 mm. Hg and containing 11.8% N corresponding to a product of Formula VIII having 11.7% N by calculation:

HaC--CC'Hs CHFCHOCHICHiIF-CH-CN (VIII) 02H;

(1)) By the same procedure, substituting for the iso valeronitrile, 1 mole of a-(N-p-vinyloxyethylamino)-isobutyronitrile, there is obtained an 86% yield of a-(N- ethoxycarbonyl -N-p-vinyloxyethylamino) isobutyronitrile of the Formula IX:

Example 15 By the procedure of Example 3 (omitting the final distillation), ethyl chloroformate (1 mole) is reacted with 1 mole of l-(B-vinyloxyethylamino)-1-cyclohexane-nitrile. The product has n =1.4632 and contains 9.9% N. It corresponds to 1- (N-ethoxycarbonyl-N-fi-vinyloxyethylamino)-cyclohexane-nitrile of Formula X having 10.4% N (theory):

Example 16 The compounds of the preceding examples are useful fungicides. For example, a spray containing a 0.1% concentration of N-fl-vinyloxyethylformamidoacetonitrile in a typical spray solvent, such as solvent naphthas, methylated naphthalenes, and so on efiects a 100% kill of Stemphylium sarcinaeforme and is nonphytotoxic to tomatoes. At a concentration in a dust formulation, this compound effects a 42% kill of rice weevils. When R in Formula I becomes a hydrocarbon or alkoxy group, the compounds become even more eflective fungicides and insecticides.

Example 17 The compounds of the preceding examples are excellent in their softening and lubricating action on such materials as leather and textiles, especially of cellulosic type. Illustratively, when the product of Example 10 is rubbed on the uppers of shoes, good flexibility is obtained.

Example 18 (a) A reaction vessel is charged with 300 grams of ethoxyethyl acetate, 35 grams of N-(p-vinyloxyethylformamido)-acetonitrile, 215 grams of methyl methacrylate, and 1.7 grams of azodiisobutyronitrile. The mixture is agitated while an inert atmosphere of nitrogen is maintained in the vessel over the reaction mixture. The contents are heated to C. and held at about this temperature for four hours. An additional charge of 0.5 gram of the azo catalyst in 35 grams of ethoxyethyl acetate is added and the polymerization is continued for an additional three hours at about 80 C. After filtration, at 80 C. under 40 pounds per square inch pressure, a substantially colorless hard polymer is obtained. A 15% solution is formed in ethoxyethyl acetate and cast to form a tough film.

(b) In similar fashion, the following mixtures are copolymerized.

(1) 50 parts of a-(N-fi-vinyloxyethylacetamido)propionitrile and 50 parts of ethyl acrylate. This polymer produces a soft film.

(2) 25 parts of p-(N-ethoxycarbonyl-N-fi-vinyloxyethylamino) propionitrile and 75 parts of acrylonitrile. Fibers and films made by extrusion of a 20% solution of this copolymer in dimethylformamide are highly resilient and more readily dyeable than the homopolymer of acrylonitrile.

(3) 10 parts of the compound of Formula IV (Example 8 (a)), 60 parts of methyl methacrylate, and 30 parts of styrene. This polymer forms a hard film.

It is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined in the appended claims.

We claim:

1. A composition of matter comprising a compound of Formula I:

CHz=CHOZNACN where Z is an alkylene group having 2 to 6 carbon atoms, the oxygen and the nitrogen being attached to different carbons thereof, A is selected from the group consisting of cyclohexylidene, --CH CH(CH -CH CH where R is an alkyl group having 1 to 8 carbon atoms and R is selected from the group consisting of methyl and ethyl, and R is selected from the group consisting of H, alkyl groups having 1 to 18 carbon atoms, phenyl, naphthyl, alkylphenyl in which the alkyl group has 1 to 4 carbon atoms, halogenated phenyl and naphthyl groups, benzyloxy, and alkoxy and alkoxyalkyl groups of the formulas R O-- and R OR Where R and R are selected from the group consisting of the same and different alkyl groups having 1 to 4 carbon atoms; with the proviso that when R is H, the two carbon atoms in A and Z that are attached directly to the N atom therebetween each carry two hydrogen atoms.

2. A composition of matter comprising an addition co polymer of a compound of Formula I as defined in claim 1 with at least one'other .copolymerizable monoethylenically unsaturated monomer.

3. A composition of matter comprising a copolymer of a compound of Formula I as defined in claim 1 with methyl methacrylate.

4. A composition of matter comprising a copolymer of a compound of Formula I as defined in claim 1 with ethyl acrylate.

5. A composition of matter comprising a copolymer of a compound of Formula I as defined in claim 1 with acrylonitrile.

6. A composition of matter comprising a copolymer of a compound of Formula I as defined in claim 1 with styrene.

7. A composition of matter comprising a-(N-fi-vinyb.

oxyethylacetamido)propionitrile.

1 1 8. A composition of matter ethylformamidoacetonitrile.

9. A composition of matter comprising p-(N-ethoxy carbonyl-N-p-vinyloxyethylamino)propionitrile. p 10. A composition of matter comprising a-(N-ethoxycarbonyl-N-fl-vinyloxyethylamino)isobutyronitrile.

11. A composition of matter comprising a compound of Formula V: 7

comprising N-p-vinyloxyl (V) OH10 CH3 A a a a a 12 claim 1 and X is selected from the group consisting of chlorine and bromine with a compound of Formula II:

(H) CH2=CHOZNHACN wherein Z and A are as defined'in claim 1.

13. A method for producing a compound of Formula I as defined in claim 1 which comprises reacting a compound of Formula. H as idefined in claim 12 with a member selected firom'the group consisting of alkyl ionmates and alkyl a-methoxyacetates.

'14. A method for producing a compound of Formula I as defined in claim 1 which comprises reacting a member selected from the-group consisting of benzyl chlorofol-mates and alkyl chloroformates in which the alkyl group has 1 to 4 carbon atoms, with a compound of Formula II as defined in claim 12.

No references cited. 

1. A COMPOSITION OF MATTER COMPRISING A COMPOUND OF FORMULA I:
 5. A COMPOSITION OF MATTER COMPRISING A COPOLYMER OF A COMPOUND OF FORMULA I AS DEFINED IN CLAIM 1 WITH ACRYLONITRILE. 